CN1100003A - Compound adsorbent and its preparing process - Google Patents
Compound adsorbent and its preparing process Download PDFInfo
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- CN1100003A CN1100003A CN 93112149 CN93112149A CN1100003A CN 1100003 A CN1100003 A CN 1100003A CN 93112149 CN93112149 CN 93112149 CN 93112149 A CN93112149 A CN 93112149A CN 1100003 A CN1100003 A CN 1100003A
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- adsorbent
- attapulgite
- carbon
- new type
- crust amine
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Abstract
The compound adsorbent containing chitinamine, attapulgite, activated carbon, fibrous yarn and zeolite powder has both high adsorption capacity the powdered carbon has and better permeability the granular carbon has, so having shorter balancing time and adapting industrial application. In addition, it has better selective adsorption, dissolubility, dispersity and packing nature, so it may be made into different shapes used in various fields.
Description
The present invention relates to a kind of compound adsorbent that contains crust amine, natural attapulgite, active carbon, cellulose and zeolite powder, be applicable to industries such as national defence, chemical industry, metallurgy, light industry, cigarette, food, environmental protection.
At present, adsorbent commonly used mainly contains active carbon, also has atlapulgite, silica gel, diatomite, activated alumina and attapulgite etc. in addition.What consumption was big, development is fast is active carbon, is divided into compacting charcoal that granularity can reach 4mm less than graininess charcoal and the particle diameter of 80 purpose powdery carbons, particle diameter 0.5-2mm etc.
Just the someone studied active carbon loading silver as far back as 1948, to change the absorption property of active carbon, made its existing absorption have the function of sterilization, this active carbon to be used for removing in drinking-water is handled again to smell, decolouring, deironing and sterilization, had obtained certain popularization.
Set up the new Adsorption Model except the further investigation adsorption theory now, more note the research of new adsorbent.Since the sixties, states such as Japan are just at research multifunctional active carbon, NACF, make charcoal felt, charcoal cloth with it again, though expanded the Application of Brand Active Carbon scope, but this NACF generally be stick with glue artificial silk be the raw material high temperature carbonization, the activation form, complex process, cost height apply being subjected to certain limitation.
With divinylbenzene and ethene is raw material, in the presence of organic solvents such as toluene, and the resin that the method by suspension copolymerization makes with absorption property, this resin based on organic matter is referred to as polymeric adsorbent.
The non-crystalline oxide compound adsorbent that the Japanese is studying has been selected SiO
2-TiO
2, SiO
2-Mgo, Al
2O
3-SiO
2, Al
2O
3Several groups of inorganic oxides of-Mgo carry out drying, pulverizing, screening to various prescriptions respectively and calcination is handled, and are used for treatment of dyeing and printing, and result of the test is thought Al
2O
3-Mgo and active carbon carry out compound, may develop rising high performance adsorbent, but up to the present, not have new progress in this respect.
File shows through patent office searching: the cellulosic that relates to is the sorbing material of raw material, as application number is 86108141 inventions that are called fibred filter filling and production method thereof: it is characterized in that fibred filter filling adopts abaca and crust glue to mix and stir and forms, weight is 1: 0.5～0.7, and crust glue to be the water that contains 3% chitin and 1% glacial acetic acid and 96% form.
And application number is the 90108994.X particulate sorbent smoke filter, though related to active carbon, materials such as sea big gun stone are manufactured adsorbent, but this adsorbent is by hot-melt adhesive, dystectic polyethylene glycol or latex binder (as PVA) or various polyester adhesive is bonding forms.
And some external patents involved be active carbon to be applied to during cigarette filter chews with electrostatic methods, have plenty of the adsorbent of forming with crust amine or chitin and crust amine blends, have plenty of with crust amine, cellulose, viscosity starch and make.
Some complex process of above adsorbent, cost height are not easy to promote; Some adsorbent permeability is poor, easily produces charcoal and leaks, and commercial Application is very limited; Some adsorption capacity is little, adsorption rate slow, it is long to reach time for adsorption balance, so range of application also is restricted.
The object of the present invention is to provide a kind of compound adsorbent, it is big to make it to possess the burgy adsorption capacity, reach the short characteristics of equilibration time, it is good to possess a charcoal permeability again, be convenient to the characteristics of commercial Application, overcome the shortcoming of the two again, this adsorbent also has the better chemical absorption property in addition, absorption property to the polarity larger molecular organics is more superior, and be convenient to be molded into granular, cotton-shaped, column and paper shape, can be widely used in industries such as national defence, chemical industry, metallurgy, light industry, cigarette, food, environmental protection.
Specific embodiments of the present invention and feature are as follows: this adsorbent contains several compositions of crust amine, natural attapulgite, active carbon, cellulose and zeolite powder, because the special construction of attapulgite, has good selection absorption property after activated, the powdered activated carbon that adds wide spectrum increases adsorption activity, utilize solubility, dispersiveness and the packing performance of crust amine, under certain condition, several composition glue are connected together, can be made into cotton-shaped, irregular granular or column.Also can copy into page.
Crust amine is obtained by the hydrolysis chitin.Natural chitin is water insoluble, aqueous slkali and dilute acid soln, after a part or most of acetyl group are sloughed in hydrolysis, dissolves in hydrochloric acid, formic acid or acetate, obtains the colloidal solution with certain viscosity.
The crystal habit of attapulgite is bar-shaped, fibrous, its crystallization is by two individual compositions, connect by oxygen atom between the individuality, and formation is used hydrochloric acid activation along the passage of wide about 0.37 * 0.6 nanometer of C shaft section (nm), get through passage and remove soluble impurity in other hole, form a large amount of micropores, thereby have absorption property, concerning certain type attapulgite, has relative size micropore relatively uniformly, so select absorption property good.
Wood pulp or straw pulp cellulose are discongested through making beating, can copy paper according to a conventional method.
Reaction mechanism is as follows: several compositions of attapulgite, active carbon and cellulose mixed in proportion, makes certain density slip, since differences such as each component proportion, granularity, form, very fast layering.And after adding a certain amount of crust amine aqueous solution, because the dispersiveness of crust amine, it can be equably attached to attapulgite, micro activated carbon particle and cellulose surface, again since it be chain macromolecule and have viscosity, subparticle and cellulose gum can be linked up.Change the proportioning of each component, its product then can be made into irregular granular, column, also can copy into page, cardboard.
Technological process of the present invention is as follows:
One, attapulgite is levigate below (300 order).
Two, with-300 purpose attapulgite powder in the hydrochloric acid of 4-10% stirring reaction 5-12 hour, activate to improve absorption property.Also the sulfuric acid treatment 5-10 of available 3-7% hour.
Three, will react and finish the back and left standstill 24 hours with-300 order slips that conventional method is difficult to carry out Separation of Solid and Liquid, the precipitation hypsokinesis goes out supernatant, can carry out the wet type batching, removes separation circuit from.
Four, with the wood pulp that also can not bleach (or straw pulp or half and half) of bleaching, fully discongest, reach button degree of separating 40-45 degree, weight in wet base 6-9 gram through slurrying.
Five,, can make the firm more of each component combination and improve the absorption property of the multiple agent of compound suction because under equal consumption, full-bodied crust amine can improve the 5-10% material recovery rate.The used crust amine of the present invention is different from 1% concentration that the NaoH of at present commercially available usefulness 40% was obtained at 100 ℃ of following hydrolysis chitins in 24 hours, viscosity＜200CP(centipoise) solution (NDJ-1 type rotary viscosimeter is measured down for 20 ℃), but chitin is immersed in 45% the NaoH solution, normal temperature 20-25 ℃ following hydrolysis 100-120 hour, or the crust amine product of 60 ℃ of viscosity＞500CP that obtained in hydrolysis 80-90 hour.
Six, with formic acid, acetate or dissolving with hydrochloric acid crust amine, be made into the solution of 1-3% concentration, preferably be made into 1-1.5% concentration with acetate and be advisable, the solution pH value that is made into is 2-7, is best with 4-5, the solution viscosity＞500CP of 1% concentration.
Seven, the cellulose that will discongest adds in half of required water, stir half of scattering, adding required crust amine aqueous solution stirred 30 minutes.
Eight, commercially available-200 purpose active carbons and the good attapulgite powder of activation are added to stir in second half water scatter, add second half crust amine aqueous solution again and stirred 30 minutes.
Nine, then with " 7 ", " 8 " described two kinds of mixed solutions merge and stirred 60 minutes, obtain to contain the slip of 1-5% solid concentration, are the best with 1-2% concentration.
Ten, the size performance that has reacted is fine, and leaving standstill can incline afterwards in 60 minutes supernatant, uses 80-100 order filter cloth to filter then, 50-80 ℃ of oven dry down, in order to prevent to tie admittedly, will constantly stir in the drying course again.
Compound adsorbent formula rate of the present invention is:
1. powdered activated carbon (100～-200 order) 15～70%(is selected by the purposes of adsorbent, and no specific (special) requirements ratio can be more greatly).
2. cellulose (natural or artificial) 20～73%(is selected by the purposes and the form of adsorbent, and as becoming page, then ratio wants＞50%).
3. crust amine (being dissolved into 1～3% solution uses) 6～15%(is selected by the intensity of adsorbent, the desired strength height, then ratio wants big).
4. attapulgite powder (100～-200 order) 3～10%(is selected by absorption property, requires the high ratio of selectivity to want big).
5. zeolite powder: (100～-200) 3～10%(can make the transition and also can not make the transition, and is selected by performance of the adsorbent, requires the high ratio of selectivity to want big).
Embodiments of the invention are as follows:
Embodiment one:
Technical recipe: wood pulp cellulose 44%
Powdered activated carbon (200 order) 42%
Crust amine 8%
Attapulgite 3%
Zeolite powder 3%
By technological process and operating condition, made the average quantitatively carbon paper of 36g/m, productive rate 75%, it is feasible to copy the paper operation, carbon paper tensile strength 71.5kg/cm.
In order to illustrate and compare the physical and chemical performance of carbon paper, powdery and granular active carbon tested simultaneously for ease of narration do following simplification:
Carbon paper-contain the carbon paper of powdered activated carbon 42% is cut into the row culture sample of the wide 30～50mm of 0.8-1mm.
Powder C-powdered activated carbon (100%) SILVER REAGENT (200 order)
Grain C-granular active carbon, SILVER REAGENT (0.2～2mm)
1. the ρ of three kinds of adsorbents
t, ρ
pAnd ε
pThe data contrast sees Table 1
As can be seen from the table, the pore structure of carbon paper, specific area have all had improvement than burgy and grain charcoal, promptly possessed burgy absorption property good (specific area is big) and the good advantage of grain charcoal permeability, overcome burgy permeability difference and the relatively poor weakness of grain charcoal adsorptivity again.
2. electrical method test:
Be filled in φ 25 * 135mm(effective dimensions after the adsorbent of three kinds of equivalent (4g) soaked with distilled water) adsorption column in, with graphite rod as anode, iron wire as negative electrode, effectively length is 100mm, die opening 15mm, the carbon paper sample can be measured 300～420MV DC voltage between the two poles of the earth before energising, and grain charcoal post can not surveyed, and the burgy post has only several millivolts, illustrate to have a large amount of dissociable active genes in the carbon paper, this characteristic has improved the chemical adsorptivity of carbon paper.
3. absorption property test:
The main adsorption capacity of surveying adsorbent to iodine, phenol and methylene blue in the liquid phase:
Iodine number:
Each 1g adds respectively in the iodine solution of respectively adorning 100ml0.096N with adsorbent, stirs to tremble after 2 hours and filters, and records the residual iodine amount of filtrate, calculates the adsorption capacity of adsorbent under this condition and sees Table 2.
Iodine number is represented the adsorption efficiency of adsorbent to the liquid phase small-molecule substance.
As shown in Table 2, burgy iodine number maximum, the carbon paper minimum, but the adsorption capacity that contains the carbon paper of charcoal 42% is equivalent to the adsorptive value of 56% powdered carbon, illustrates that carbon paper has improved the absorption property of iodine.
(2) phenol value:
Method of testing is the same, and test result sees Table 3.
Phenol value representation adsorbent is to organic adsorption efficiency in the liquid phase.As seen from Table 3, the phenol value maximum of powder C, patient paper takes second place, grain C minimum, illustrate contain C only 42% carbon paper phenol value 100% grain C of weight such as surpassed and be equivalent to the adsorption capacity of burgy 84%, illustrate that carbon paper has improved the absorption property of phenol or illustrate that it is more suitable for adsorb organic compound matter.
(3) methylene blue decolorizing ability:
Table 3 phenol value test result
| The adsorbent project | Phenol solution consumption ml | Phenol concentration consumption ml | Adsorbent consumption g | Filtrate phenol concentration mg/l | Adsorption capacity (phenol value) mg/l |
| Powder C | 100 | 2 | 1 | 1.024 | 97.6 |
| Powder C | 100 | 2 | 1 | 1.203 | 79.7 |
| Carbon paper | 100 | 2 | 1 | 1.175 | 82.5 |
Method of testing is the same, and test result sees Table 4.
The table with test results of table 4 pair methylene blue decolorizing ability
| The adsorbent project | Methylene blue solution consumption ml | Methylene blue concentration g/l | Adsorbent consumption g | Methylene blue concentration g/l in the filtrate | Adsorption capacity mg/l |
| Powder C | 200 | 2.5 | 1 | 0.835 | 97.6 |
| Powder C | 200 | 2.5 | 1 | 1.920 | 79.7 |
| Carbon paper | 200 | 2.5 | 1 | 1.175 | 82.5 |
The methylene blue decolorizing ability is represented the adsorption efficiency of adsorbent to macromolecular substances, as seen, C is the highest for powder from table 4, and carbon paper takes second place, grain C minimum, it is bigger that numerical value differs, and powder C is 1.6 times of carbon paper, is 2.87 times an of C, and carbon paper is 1.79 times of a C, and the adsorption capacity that contains the carbon paper of charcoal 42% is 62% of powder C, illustrates that carbon paper that compound adsorbent makes has surpassed raw meal C to the adsorption capacity of methylene blue, has illustrated that also compound adsorbent has adsorption rate preferably to macromolecular substances.
Embodiment 2:
Make carbon paper by following prescription:
Wood pulp cellulose 20%
Active carbon (200 order) 66%
Crust amine 8%
Attapulgite 3%
Zeolite powder 3%
Carbon paper is cut into little of 2-3mm is filled in the adsorption column, handle the reactive brilliant blue K-GR dyes of anthraquinone solution that contains 500mg/l, outflow liquid is almost colourless.
Embodiment 3:
Make column, irregular granular by following prescription:
Wood pulp cellulose 20%
Powdered activated carbon (200 order) 60%
Crust amine 7%
Attapulgite 8%
Zeolite powder 5%
Processing contains gold and leaches the expensive liquid of gold mine for the cyaniding of 10mg/l, and the gold recovery rate is more than 99%.
Example four:
Do and copy paper roll cigarette filter and chew:
Cellulose 68%
Active carbon 20%
Crust amine 6%
Attapulgite 3%
Zeolite powder 3%
Manufacture paper with pulp into the plain weave carbon paper, fracture length can reach 3000m, tensile strength＞2kg/cm
Manufacture paper with pulp into wrinkle, fracture length can reach 500m, tensile strength＞1.5kg/cm
Embodiment 5:
Press wood pulp cellulose 60%
Active carbon 15%(-200 order)
Attapulgite 10%
Zeolite powder 9%
Crust amine 6%
Make the disposable moisture absorption and inhale smelly shoe-pad, can the absorbing sweat deodorizing.
Embodiment 6:
Cellulose 40%
Active carbon 40%(-200 order)
Crust amine 10%
Attapulgite 5%
Zeolite powder 5%
Make cotton-shaped or copy paper and be used for anti-poison respirator, can play good gas defence effect.The Chemical Manufacture and other production industry that can be used for paint production, spray painting operation and produce bad smell.
Compound adsorbent involved in the present invention, no matter be to copy paper or make cotton-shaped, column, irregular granular, all available conventional equipment is finished, therefore, drop into few, the instant effect of development capital, especially attapulgite, zeolite powder all belong to natural material, and price is honest and clean, cost is low, for the every profession and trade large-scale application provides wide prospect.
Claims (5)
1, a kind of NEW TYPE OF COMPOSITE adsorbent is characterized in that: this adsorbent is formulated by a certain percentage by powdered activated carbon, cellulose, natural attapulgite, crust amine, zeolite powder.
2, NEW TYPE OF COMPOSITE adsorbent according to claim 1, it is characterized in that: this compound adsorbent is chosen scope according to range of application different formulations ratio and is: powdered activated carbon 15-70%, cellulose 20-73%, crust amine 6-15%, natural attapulgite 3-10%, zeolite powder 3-10%.
3, NEW TYPE OF COMPOSITE adsorbent according to claim 1 is characterized in that: attapulgite is milled down to-300 orders, and stirring reaction activated in the hydrochloric acid of 4～10% concentration in 5～12 hours.
4, NEW TYPE OF COMPOSITE adsorbent according to claim 1 is characterized in that: chitin is to be immersed in the NaoH solution of 45% concentration, and (20～25 ℃) hydrolysis 100-120 hour or 60 ℃ are hydrolysis 80-90 hour under the normal temperature.
5, NEW TYPE OF COMPOSITE adsorbent according to claim 4 is characterized in that: the crust amine aqueous solution viscosity＞500CP of 1% concentration.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 93112149 CN1100003A (en) | 1993-09-05 | 1993-09-05 | Compound adsorbent and its preparing process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 93112149 CN1100003A (en) | 1993-09-05 | 1993-09-05 | Compound adsorbent and its preparing process |
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| Publication Number | Publication Date |
|---|---|
| CN1100003A true CN1100003A (en) | 1995-03-15 |
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| CN 93112149 Pending CN1100003A (en) | 1993-09-05 | 1993-09-05 | Compound adsorbent and its preparing process |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101438851B (en) * | 2008-12-29 | 2011-08-31 | 浙江中烟工业有限责任公司 | Method for reducing dry sensation of cigarette smoke |
| CN101898115B (en) * | 2009-05-25 | 2011-09-21 | 周奇迪 | Filter medium, preparation method thereof, filter element and water purification device |
| CN106861659A (en) * | 2017-04-12 | 2017-06-20 | 明光市国星凹土有限公司 | A kind of attapulgite oil product decolorising agent for water process and preparation method thereof |
| CN106944000A (en) * | 2017-04-19 | 2017-07-14 | 句容市百诚活性炭有限公司 | A kind of acticarbon and preparation method thereof |
| CN108716156A (en) * | 2018-04-23 | 2018-10-30 | 句容市兴武包装有限公司 | A kind of preparation method of deodorization paper |
| CN108968134A (en) * | 2018-06-08 | 2018-12-11 | 李华 | A kind of composition for substituting conventional cigarette and helping to give up smoking |
-
1993
- 1993-09-05 CN CN 93112149 patent/CN1100003A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101438851B (en) * | 2008-12-29 | 2011-08-31 | 浙江中烟工业有限责任公司 | Method for reducing dry sensation of cigarette smoke |
| CN101898115B (en) * | 2009-05-25 | 2011-09-21 | 周奇迪 | Filter medium, preparation method thereof, filter element and water purification device |
| CN106861659A (en) * | 2017-04-12 | 2017-06-20 | 明光市国星凹土有限公司 | A kind of attapulgite oil product decolorising agent for water process and preparation method thereof |
| CN106944000A (en) * | 2017-04-19 | 2017-07-14 | 句容市百诚活性炭有限公司 | A kind of acticarbon and preparation method thereof |
| CN108716156A (en) * | 2018-04-23 | 2018-10-30 | 句容市兴武包装有限公司 | A kind of preparation method of deodorization paper |
| CN108968134A (en) * | 2018-06-08 | 2018-12-11 | 李华 | A kind of composition for substituting conventional cigarette and helping to give up smoking |
| CN108968134B (en) * | 2018-06-08 | 2022-02-25 | 李华 | A composition for replacing conventional cigarette and helping quit smoking |
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